The present invention is directed to compositions for oxidation dyeing of keratin fibres comprising (a) at least one oxidation base, (b) at least one coupler chosen from 2-substituted 5-aminoalkylphenol derivatives and the acid addition salts thereof, and (c) at least one additional coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers and the acid addition salts thereof, in a medium suitable for dyeing. The inventive compositions can be used for oxidation dyeing of human keratin fibres such as hair. The present invention is also directed to dyeing processes using these compositions.
Dye compositions comprising oxidation dye precursors are known in the art for dyeing keratinous fibres, in particular human hair. These oxidation dye precursors include ortho-phenylenediamines, para-phenylenediamines, ortho-aminophenols, para-aminophenols and heterocyclic bases. These are generally known as oxidation bases. The oxidation dye precursors, or oxidation bases, are generally colorless or weakly colored compounds which may give rise to colored compounds and dyes when combined with oxidizing products via oxidative condensation.
The shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers. Such coloration modifiers may, for example, be chosen from aromatic meta-diamines, aromatic meta-aminophenols, aromatic meta-diphenols and certain heterocyclic compounds. The variety of oxidation bases and couplers may allow a wide range of colors to be obtained.
The so-called xe2x80x9cpermanentxe2x80x9d coloration obtained from using these oxidation dyes should have at least one of the following desirable characteristics. The coloration should have no toxicological drawbacks, the shades obtained should have the desired intensity, and the coloration should have good resistance to external agents to which the fibres may be subjected such as light, bad weather, washing, permanent-waving, perspiration and rubbing. The dyes should allow coverage of grey hair and should be as unselective as possible, that is, they should allow only the smallest possible differences in coloration along the same keratinous fibre which may be differently sensitized (i.e. damaged) between its tip and its root.
Also known in the art are dye compositions containing 2-substituted 5-aminoalkylphenol derivatives for use as couplers. These may be in combination with one or more oxidation bases chosen from, for example, certain para-phenylenediamines, para-aminophenol, para-methylaminophenol, ortho-aminophenol and certain heterocyclic oxidation bases such as 2,5-diaminopyridine and tetraaminopyrimidine. Such dye compositions have been proposed, for example, in patent application JP-2 521 636, the disclosure of which is incorporated herein by reference. However, the colorations obtained using these compositions may not always be sufficiently strong, chromatic and/or resistant to various external agents to which the fibres may be subjected.
The inventors have now discovered that by combining (i) at least one oxidation base, (ii) at least one coupler chosen from 2-substituted 5-aminoalkylphenol derivatives of formula (I) as defined below and the acid addition salts thereof and (iii) at least one additional coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers and the acid addition salts thereof, it may be possible to obtain novel dyes which may result in chromatic, strong, aesthetic colorations in a variety of shades, which may be mainly unselective and which may show satisfactory resistance to one or more external agents to which the fibres may be subjected.
Specifically, one subject of the present invention is compositions for oxidation dyeing of keratin fibres comprising:
(a) at least one oxidation base;
(b) at least one coupler chosen from 2-substituted 5-aminoalkylphenol derivatives of formula (I) and the acid addition salts thereof: 
wherein:
R1 is chosen from hydrogen atoms and C2-C5 acyl groups, optionally substituted;
R2 is chosen from hydrogen atoms, C1-C4 alkyl groups, optionally substituted, C1-C4 alkoxy groups, optionally substituted, and amino groups, optionally substituted;
R3 is chosen from hydrogen atoms, halogen atoms, C1-C4 alkoxy groups and C1-C4 monohydroxyalkoxy groups; and
R4 is chosen from C1-C4 alkyl groups; and
(c) at least one additional coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers and the acid addition salts thereof, in a medium suitable for dyeing. For example, the keratin fibres may be human keratin fibres, such as hair.
By virtue of the present invention, it may be possible to obtain chromatic, strong, aesthetic colorations in a variety of shades which may show low selectivity and may show excellent properties of withstanding not only at least one atmospheric agent (such as light and bad weather) but may also withstand perspiration and/or various treatments to which the hair may be subjected.
Another subject of the present invention is processes for oxidation dyeing of keratin fibres using the inventive compositions.
The nature of the at least one oxidation base that may be used in the present invention is not a critical factor. For example, the at least one oxidation base can be chosen from para-phenylenediamines, double bases, para-aminophenols, ortho-aminophenols, heterocyclic oxidation bases and the acid addition salts of any of the foregoing at least one oxidation bases.
For example, the para-phenylenediamines suitable for use in the present invention can be chosen from compounds of formula (II) and the acid addition salts thereof: 
wherein:
R5 is chosen from hydrogen atoms, C1-C4 alkyl groups, C1-C4 monohydroxyalkyl groups, C2-C4 polyhydroxyalkyl groups, (C1-C4)alkoxy(C1-C4)alkyl groups, C1-C4 alkyl groups substituted with at least one nitrogen-containing group, phenyl groups and 4xe2x80x2-aminophenyl groups;
R6 is chosen from hydrogen atoms, C1-C4 alkyl groups, C1-C4 monohydroxyalkyl groups, C2-C4 polyhydroxyalkyl groups, (C1-C4)alkoxy(C1-C4)alkyl groups and C1-C4 alkyl groups substituted with at least one nitrogen-containing group;
R7 is chosen from hydrogen atoms, halogen atoms such as a chlorine, bromine, iodine or fluorine atom, C1-C4 alkyl groups, C1-C4 monohydroxyalkyl groups, C1-C4 hydroxyalkoxy groups, acetylamino(C1-C4)alkoxy groups, C1-C4 mesylaminoalkoxy groups and carbamoylamino(C1-C4)alkoxy groups; and
R8 is chosen from hydrogen atoms, halogen atoms and C1-C4 alkyl groups.
Non-limiting examples of nitrogen-containing groups comprised in groups of formula (II) include amino groups, mono(C1-C4)alkylamino groups, di(C1-C4)alkylamino groups, tri(C1-C4)alkylamino groups, monohydroxy(C1-C4)alkylamino groups, imidazolinium groups and ammonium groups.
In one embodiment, compounds of formula (II) are chosen from para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-amino-N,N-bis(xcex2-hydroxyethyl)-2-methylaniline, 4-amino-2-chloro-N,N-bis(xcex2-hydroxyethyl)aniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl-xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, N-(xcex2-methoxyethyl)-para-phenylenediamine
In another embodiment, compounds of formula (II) are chosen from para-phenylenediamine, and the acid addition salts of any of the foregoing.
In another embodiment, compounds of formula (II) are chosen from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine and the acid addition salts of any of the foregoing.
As used herein, xe2x80x9cdouble basesxe2x80x9d means compounds comprising at least two aromatic rings bearing at least one group chosen from amino groups and hydroxyl groups.
According to the present invention, double bases which may be used as the at least oxidation base can be chosen from compounds of formula (III) and the acid addition salts thereof: 
wherein:
Z1 and Z2, which may be identical or different, are each chosen from hydroxyl groups, xe2x80x94NH2 groups, optionally substituted with at least one entity chosen from C1-C4 alkyl groups and linker arms Y as defined below;
linker arm Y is chosen from linear and branched alkylene chains comprising from 1 to 14 carbon atoms, wherein said alkylene chains are optionally interrupted by at least one entity chosen from nitrogen-containing groups and heteroatoms such as oxygen atoms, sulphur atoms and nitrogen atoms, wherein said alkylene chains are optionally terminated with at least one entity chosen from nitrogen-containing groups and heteroatoms such as oxygen atoms, sulphur atoms and nitrogen atoms, and wherein said alkylene chains are optionally substituted with at least one group chosen from hydroxyl groups and C1-C6 alkoxy groups;
R9 and R10, which may be identical or different, are each chosen from hydrogen atoms, halogen atoms, C1-C4 alkyl groups, C1-C4 monohydroxyalkyl groups, C2-C4 polyhydroxyalkyl groups, C1-C4 aminoalkyl groups and linker arms Y;
R11, R12, R13, R14, R15 and R16, which may be identical or different, are each chosen from hydrogen atoms, linker arms Y and C1-C4 alkyl groups;
with the proviso that said compounds of formula (III) comprise only one linker arm Y per molecule.
Non-limiting examples of said nitrogen-containing groups comprised in compounds of formula (III) include amino groups, mono(C1-C4)alkylamino groups, di(C1-C4)alkylamino groups, tri(C1-C4)alkylamino groups monohydroxy(C1-C4)alkylamino groups, imidazolinium groups and ammonium groups.
In one embodiment, double bases of formula (III) above are chosen from N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)-tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)-tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis-(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and the acid addition salts of any of the foregoing.
In another embodiment, double bases of formula (III) are chosen from N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and the acid addition salts of any of the foregoing.
According to the present invention, para-aminophenols which can be used as the at least one oxidation base can be chosen from compounds of formula (IV) and the acid addition salts thereof: 
wherein:
R17 is chosen from hydrogen atoms, halogen atoms, C1-C4 alkyl groups, C1-C4 monohydroxyalkyl groups, (C1-C4)alkoxy(C1-C4)alkyl groups, C1-C4 aminoalkyl groups and hydroxy(C1-C4)alkylamino-(C1-C4)alkyl groups;
R18 is chosen from hydrogen atoms, halogen atoms, C1-C4-alkyl groups, C1-C4 monohydroxyalkyl groups, C2-C4 polyhydroxyalkyl groups, C1-C4 aminoalkyl groups, C1-C4 cyanoalkyl groups and (C1-C4)alkoxy-(C1-C4)alkyl groups;
with the proviso that at least one of said R17 and R18 is chosen from hydrogen atoms.
In one embodiment, para-aminophenols of formula (IV) are chosen from para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol and the acid addition salts thereof.
According to the present invention, ortho-aminophenols which can be used as the at least one oxidation base can be chosen from 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol and the acid addition salts thereof.
The heterocyclic bases which can be used as the at least one oxidation base can be chosen from pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and the acid addition salts thereof.
For example, pyridine derivatives can be chosen from those described in patents GB 1,026,978 and GB 1,153,196, the disclosures of which are incorporated herein by reference, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine and the acid addition salts thereof.
Pyrimidine derivatives can be chosen, for example, from those described in patents DE 2 359 399, JP 88-169 571, JP 05 163 124, EP 0 770 375 and patent application WO 96/15765, the disclosures of which are incorporated herein by reference, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048, the disclosure of which is incorporated herein by reference, such as pyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, pyrazolo[1,5-a]pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine, 3-aminopyrazolo[1,5-a]pyrimidin-7-ol, 3-aminopyrazolo[1,5-a]pyrimidin-5-ol, 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine, the acid addition salts of any of the foregoing and the tautomeric forms of any of the foregoing when a tautomeric equilibrium exists.
According to the present invention, pyrazole derivatives can be chosen from those described in patents DE 3,843,892, DE 4,133,957 and patent applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988, the disclosures of which are incorporated herein by reference, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole and the acid addition salts of any of the foregoing.
Suitable 2-substituted 5-aminoalkylphenol derivatives of formula (I) according to the present invention, the synthetic intermediates thereof and processes for preparing them are described in patent application JP-2 521 636, the disclosure of which is incorporated herein by reference.
As previously mentioned, said R2 and said R4 of the formula (I) may be chosen from C1-C4 alkyl groups. Non-limiting examples of said C1-C4 alkyl groups include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups and tert-butyl groups.
Further, said R2 and said R3 of formula (I) may be chosen from optionally substituted C1-C4 alkoxy groups. Non-limiting examples of C1-C4 alkoxy groups include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, sec-butoxy groups and tert-butoxy groups.
Said R1 of formula (I) may be chosen from optionally substituted C2-C5 acyl groups. Non-limiting examples of C2-C5 acyl groups include acetyl groups, propanoyl groups, 2,2-dimethylpropanoyl groups, 3-methylpropanoyl groups, butanoyl groups, 2-methylbutanoyl groups and pentanoyl groups.
According to the present invention, said R3 may be chosen from halogen atoms. Non-limiting examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.
In one embodiment, said R1 is chosen from hydrogen atoms, acetyl groups and propanoyl groups, said R2 is chosen from methyl groups, ethyl groups, methoxy groups and amino groups, said R3 is chosen from hydrogen atoms and methoxy groups, and said R4 is chosen from methyl groups and ethyl groups.
Non-limiting examples of substituents on said C1-C4 alkyl groups, C1-C4 alkoxy groups and C2-C5 acyl groups comprised in formula (I) include halogen atoms (such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms), C1-C4 alkoxy groups (such as methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, sec-butoxy groups and tert-butoxy groups), C2-C5 alkanoyloxy groups (such as acetoxy groups, propanoyloxy groups, 2,2-dimethylpropanoyloxy groups, 3-methylpropanoyloxy groups, butanoyloxy groups, 2-methylbutanoyloxy groups and pentanoyloxy groups), hydroxyl groups, amino group, amino groups protected with at least one protecting group, carboxyl groups and C2-C5 alkoxycarbonyl groups (such as methoxycarbonyl groups, ethoxycarbonyl groups, n-propoxycarbonyl groups, isopropoxycarbonyl groups, n-butoxycarbonyl groups, sec-butoxycarbonyl groups and tert-butoxycarbonyl groups). In one embodiment substituents are chosen from methoxy groups and hydroxyl groups.
For example, said at least one protecting group can be chosen from tert-butoxycarbonyl groups and benzyloxycarbonyl groups.
As previously mentioned, said R2 can be chosen from substituted amino groups. Non-limiting examples of substituents which may be used according to the present invention include C1-C4 alkyl groups optionally substituted with at least one hydroxyl group. In one embodiment, the substituents are chosen from hydroxyethyl groups.
In another embodiment, said 2-substituted 5-aminoalkylphenol derivatives of formula (I) are chosen from:
N-(2-hydroxy-4-methylphenyl)formamide,
N-(2-hydroxy-4-methylphenyl) methylcarbamate,
N-(2-hydroxy-4-methylphenyl)urea,
N-(2-hydroxy-4-methylphenyl)-Nxe2x80x2-(2-hydroxyethyl) urea,
N-(2-hydroxy-4-methylphenyl)acetamide,
N-(2-hydroxy-4-methylphenyl)chloroacetamide,
N-(2-hydroxy-4-methylphenyl)acetoxyacetamide,
N-(2-hydroxy-4-methylphenyl)hydroxyacetamide,
N-(2-hydroxy-4-methylphenyl)methoxyacetamide,
N-(2-hydroxy-4-methylphenyl)aminoacetamide,
N-(2-hydroxy-4-methylphenyl)propionamide,
N-(2-hydroxy-4-methylphenyl)-2-hydroxypropionamide,
N-(2-hydroxy-4-methylphenyl)-3-aminopropionamide,
N-(2-hydroxy-4-methylphenyl)butanamide,
N-(2-hydroxy-4-methylphenyl)-4-chlorobutanamide,
N-(2-hydroxy-4-methylphenyl)succinamide,
N-(2-hydroxy-4-isopropylphenyl)acetamide,
2xe2x80x2-acetamido-5xe2x80x2-methylphenyl acetate,
2xe2x80x2-propionamido-5xe2x80x2-methylphenyl propionate,
N-(2-hydroxy-5-methoxy-4-methylphenyl)acetamide, and
the acid addition salts of any of the foregoing.
According to the present invention, said meta-phenylenediamines, meta-aminophenols and meta-diphenols which may be used as the least one additional coupler can be chosen from compounds of formula (V) and the acid addition salts thereof: 
wherein:
A and B, which may be identical or different, are each chosen from hydroxyl groups, amino groups and xe2x80x94NHR22 groups wherein R22 is chosen from C1-C4 alkyl groups, C1-C4 monohydroxyalkyl groups and C2-C4 polyhydroxyalkyl groups;
R19, R20 and R21, which may be identical or different, are each chosen from hydrogen atoms, halogen atoms such as bromine atoms, chlorine atoms, iodine atoms and fluorine atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 monohydroxyalkyl groups, C2-C4 polyhydroxyalkyl groups, C1-C4 monohydroxyalkoxy groups and C2-C4 polyhydroxyalkoxy groups.
In one embodiment, compounds of formula (V) are chosen from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene and the acid addition salts of any of the foregoing.
Heterocyclic couplers which may be used as the least one additional coupler can be chosen from indole derivatives, indoline derivatives, pyridine derivatives, pyrimidine derivatives, pyrazolones and the acid addition salts of any of the foregoing.
In one embodiment, heterocyclic couplers are chosen from sesamol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 6-hydroxybenzomorpholine, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one and the acid addition salts of any of the foregoing. In another embodiment, the at least one additional coupler is chosen from xcex1-naphthol and 2-methyl-1-naphthol.
In yet another embodiment of the invention, the at least one additional coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols and the acid addition salts of any of the foregoing, while in yet another embodiment, the at least so one additional coupler is chosen from compounds of formula (V).
The at least one oxidation base may be present in an amount generally ranging from about 0.0005% to about 12% by weight relative to the total weight of the composition, such as from about 0.005% to about 6% by weight.
The at least one coupler chosen from 2-substituted 5-aminoalkylphenol derivatives of formula (I) and the acid addition salts thereof may be present in an amount generally ranging from about 0.0005% to about 12% by weight relative to the total weight of the composition, such as from about 0.005% to about 6% by weight.
The at least one additional coupler may be present in an amount generally ranging from about 0.0001% to about 10% by weight relative to the total weight of the composition, such as from about 0.005% to about 5% by weight.
In general, the acid addition salts which can be used according to the present invention may be chosen from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.
According to the present invention, the inventive dye compositions may further comprise at least one direct dye.
As previously mentioned, the inventive compositions comprise a medium suitable for dyeing. The medium suitable for dyeing, which can also be considered as the support for the dyeing composition, can be chosen from water and a mixture of water and at least one organic solvent if the compounds are not sufficiently soluble in water alone. The at least one organic solvent may be chosen from C1-C4 alkanols, glycerol, glycols, glycol ethers and aromatic alcohols. Non-limiting examples of C1-C4 alkanols are ethanol and isopropanol, and examples of glycols and glycol ethers are 2-butoxyethanol, propylene to glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether. Representative aromatic alcohols are benzyl alcohol and phenoxy ethanol.
The at least one organic solvent, if present, generally ranges from 1% to about 40% by weight relative to the total weight of the composition, such as from about 5% to about 30%.
According to the present invention, the pH of the inventive composition generally ranges from about 3 to about 12, such as from about 5 to about 12. The pH may be adjusted to the desired value using acidifying or basifying agents suitable for use in compositions for dyeing of keratin fibres.
Acidifying agents which may be used according to the present invention can be chosen from inorganic acids and organic acids. For example, the acidifying agents can be chosen from hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Basifying agents which may be used according to the present invention can be chosen from aqueous ammonia, alkaline carbonates, alkanolamines such as mono-ethanolamines, di-ethanolamines and tri-ethanolamines, 2-methyl-2-amino-1-propanol and derivatives thereof, sodium hydroxide, potassium hydroxide and compounds of formula (VI): 
wherein:
W is chosen from propylene groups, optionally substituted with at least one group chosen from hydroxyl groups and C1-C4 alkyl groups; and
R23, R24, R25 and R26, which may be identical or different, are each chosen from hydrogen atoms, C1-C4 alkyl groups and C1-C4 hydroxyalkyl groups.
According to the present invention, the compositions can further comprise at least one suitable additive conventionally used in compositions for dyeing hair chosen from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, anionic polymers, cationic polymers, nonionic polymers, amphoteric polymers, zwitterionic polymers, inorganic thickeners, organic thickeners such as, for example, nonionic guar gums, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, optionally modified conditioners such as, for example, volatile and non-volatile silicones, film-forming agents, ceramides, preserving agents and opacifiers.
Needless to say, a person skilled in the art will take care to select the at least one suitable additive such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.
In the present invention, the inventive compositions can be in the form of liquids, creams, mousses or gels, which may optionally be pressurized, or in any other form which is suitable for dyeing keratin fibres, such as human hair.
As previously mentioned, another subject of the present invention is processes for dyeing keratin fibres comprising using at least one inventive composition as defined above. According to one inventive process, at least one dye composition as defined above is applied to the said keratin fibres for a sufficient time to develop a desired color. The desired color can be developed at acidic, neutral or alkaline pH using at least one oxidizing agent. Further, the at least one oxidizing agent can optionally be added to said at least one dye composition prior to use, such as immediately prior to use, and can optionally be comprised in at least one oxidizing composition. The oxidizing composition can optionally be applied to the keratin fibres simultaneously with the least one dye composition and can optionally be applied to the keratin fibres sequentially with, and separately from, the least one dye composition.
In one embodiment, the at least one dye composition is mixed, at the time of use, with at least one oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent which is present in an amount sufficient to develop a desired coloration. The resulting mixture is then applied to the keratin fibres and is left on the keratin fibres, for example, for about 3 to about 50 minutes, such as from about 5 to about 30 minutes, after which the fibres may be rinsed, washed with shampoo, rinsed again and dried.
According to the present invention, the at least one oxidizing agent may be chosen from oxidizing agents conventionally used for the oxidation dyeing of keratin fibres. Non-limiting examples of such oxidizing agents include hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, peracids and enzymes such as peroxidases, 2-electron oxidoreductases (such as uricases) and 4-electron oxygenases (such as laccases). In one embodiment, the at least one oxidizing agent is chosen from hydrogen peroxide.
The pH of the composition resulting from mixing the at least one oxidizing composition with the at least one dye composition generally ranges from about 3 to about 12, such as from about 5 to about 11. The pH of the resultant composition may be adjusted to a desired value using acidifying or basifying agents suitable for use in dyeing of keratin fibres, such as those defined above.
According to the present invention, the at least one oxidizing composition may further comprise at least one suitable additive conventionally used in dye compositions, such as those defined above.
The inventive compositions which are applied to the keratin fibres can be in the form of liquids, creams, mousses or gels, which may optionally be pressurized, or in any other form which is suitable for at least one keratinous fibre, such as human hair.
Another subject of the present invention is a multi-compartment dyeing device or kit comprising (a) a first compartment comprising a first composition and (b) a second compartment comprising a second composition, wherein said first composition comprises at least one dye composition comprising:
(a) at least one oxidation base;
(b) at least one coupler chosen from 2-substituted 5-aminoalkylphenol derivatives of formula (I) and the acid addition salts thereof: 
wherein:
R1 is chosen from hydrogen atoms and C2-C5 acyl groups, optionally substituted;
R2 is chosen from hydrogen atoms, C1-C4 alkyl groups, optionally substituted, C1-C4 alkoxy groups, optionally substituted, and amino groups, optionally substituted;
R3 is chosen from hydrogen atoms, halogen atoms, C1-C4 alkoxy groups and C1-C4 monohydroxyalkoxy groups; and
R4 is chosen from C1-C4 alkyl groups; and
(c) at least one additional coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers and the acid addition salts thereof; and wherein said second composition comprises at least one oxidizing composition as defined above. These devices may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of L""Orxc3xa9al, the disclosure of which is incorporated herein by reference.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term xe2x80x9cabout.xe2x80x9d Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The following examples are intended to illustrate the invention without limiting the scope as a result. The percentages are given on a weight basis.